Ethoxy ethyl amino phenyl azo dyestuff

ABSTRACT

WATER INSOLUBLE AZO DYESTUFFS FREE FROM SULPHONIC ACID AND CARBOXYLIC ACID GROUPS OF THE FORMULA   1-(R-N=N-),2-X,4-(R1-N(-R2)-),5-Y-BENZENE   IN WHICH R IS A RADICAL OF THE BENZENE OR HETEROCYCLIC SERIES; X IS ACYLAMINO; Y IS HYDROGEN, HALOGEN, ALKYL OR ALKOXY; R1 IS   R3-O-CH(-R7)-CH(-R6)-O-CH(-R5)-CH(-R4)-   R4, R5, R6 AND R7 ARE HYDROGENS OR LOWER ALKYL RADICALS WITH 1 TO 2 CARBONS; R3 IS HYDROGEN OR -COR8; R8 IS AN OPTIONALLY SUBSTITUTED LOWER ALKYL RADICAL; R2 IS CNH2N+1; AND N IS AN INTEGER FROM 1 TO 4. THE DYESTUFF ARE USEFUL FOR DYEING HYDROPHOBIC FIBERS, E.G. AROMATIC POLYESTERS.

United States Patent 3,586,663 ETHOXY ETHYL AMINO PHENYL AZO DYESTUFFWinfried Kruckenberg, Leverkusen, Germany, assignor to FarbenfabrikenBayer Aktiengesellschaft, Leverkusen, Germany N Drawing. Filed Apr. 12,1967, Ser. No. 630,214 Claims priority, application Germany, Apr. 19,1966, F 48,968; Oct. 7, 1966, F 50,378 Int. Cl. C07c 107/04, 107/06;C09b 29/04 U.S. Cl. 260-2071 8 Claims ABSTRACT OF THE DISCLOSURE Waterinsoluble azo dyestuffs free from sulphonic acid and carboxylic acidgroups of the formula I R1 X in which R is a radical of the benzene orheterocyclic series; X is acylamino; Y is hydrogen, halogen, alkyl oralkoxy; R, is

-( :Ht 3H0CH0H-oR3 R4 Rs Rt 1 R R R and R are hydrogens or lower alkylradicals with 1 to 2 carbons; R is hydrogen or --COR R is an optionallysubstituted lower alkyl radical; R is C H and n is an integer from 1 to4. The dyestuffs are useful for dyeing hydrophobic fibers, e.g. aromaticpolyesters.

The object of the invention comprises water-insoluble azo dyestuffs ofthe formula These valuable new dyestulfs are Obtained by coupling adiazo component of the benzene or heterocyclic series with an amine ofthe general formula a X (II) in the p-position to the group selectingstarting components which are free from sulphonic acid and carboxylicacid groups.

In the general formulae, R denotes a radical of the benzene orheterocyclic series, X is an acylamino substituent, Y stands forhydrogen, halogen, an alkyl or alkoxy group, R denotes a radical ---C,,Hwherein n stands for an integer from 1 to 4, R denotes a group -CHCHOCHOH-0Rs in in it. it, in which R R R and R are hydrogen or lower alkylradicals with 1 to 2 carbon atoms and R is hydrogen or the radical CORwherein R stands for a lower alkyl radical.

The lower alkyl radical R may be further substituted and may be present,for example, in the form of haloalkyl radicals, such as chloroethyl-;cyanoalkyl radicals,

3,586,663 Patented June 22., 1971 such as cyanoethyl-; orcarboalkoxyalkyl radicals, such as carbomethoxy- (or -ethoxy-) ethylradicals.

Coupling of the starting components is carried out in the usual manner,preferably in an acidic solution or suspension. Besides other diazocomponents of the benzene series, aniline derivatives which contain oneor more cyano groups prove to be particularly advantageous. Suitablediazo components are, inter alia:

4-cyanoaniline,

4-nitroaniline,

4-nitro-2-chloroaniline, 4-nitro-2-cyanoaniline, 2,4-dicyanoaniline,

2,4-dinitroaniline, 3-chloro-4-cyanoaniline, Z-cyano-S-chloroaniline,3,4-dicyanoaniline,

2,5-dicyanoaniline, 2,6-dichloro-4-nitroaniline,2-chloro-4-cyanoaniline, 4-amino-acetophenone, Z-amino-S-nitrotoluene,2-amino-5-nitroanisole, 3-nitro-4-aminotoluene, 2,4-dichloroaniline,2,5-dichloro-4-nitroaniline, 2-trifiuoromethyl-4-chloroaniline,3-chloro-4-amino-l-trifluoromethyl-benzene,2-cyano-4,5,6-trichloroaniline, 2,4-dinitro-6-bromo-aniline,2-cyano-4,6'dinitroaniline, 2-cyano-6-bromoor -6-chloro-4-nitroaniline,2,4-dicyano-6-chl0roaniline, 2-methoxy-4-nitroaniline,Z-amino-S-nitro-benzoic acid methyl ester, 4-aminobenzoic acidalkylamides, such as -methyl- -dimethyl-arnide,

4-amino-benzoic acid methyl ester, 3-nitro-4-aminobenzoic acid butylester, 1-aminobenzene-3- -4-methylsulphone or -ethylsulphone.

The following diazo components of the heterocyclic series prove to beparticularly valuable:

The following amines can be used as coupling components, for example:

C NHOCOHzCl ZHlO 02 .1140 (If C2135 /CHs 1 CzHrO 0211400011: NHCO CH3 III 621140 CzHqO C CzHg NHCO CH3 {I ZHtO 021340 C CH3 NHCO CH3 N C2H40011253110 OH NHC O 03H] CzHs 021140021140 C CH; NHOzS OH; H 0

CgH4OCgH40 C C2H40l NHOzS CH 02 40011140 0 on=orr NHOO OH; H O

2 4OCZH4OH NHO C CHzCl 0 1140 02114011 NBC 0 CH;

02114002114011 NHCOCHQ NBC ONH;

OCHa

CzHa

CzH 0 C 114 0 H NHCO CH3 NHCOCH:

ti O NHOzSOHa 02114002114013 NHCO CH3 The above process for theproduction of the new azo dyestuffs can also be modified in that theformation of the terminal acyloxy group OOCR is carried out only at thefinal stage of the process, ie after coupling the diazo compound and theaniline coupling component containing, in this case, a hydroxyalkoxyalkyl group, or that an acylamino group X is converted at thefinal stage of the process into an acylamino group of different type byselective hydrolysis and re-acylation.

The dyestuffs which can be obtained according to the present process areeminently suitable for the dyeing and printing of hydrophobic materials,especially of textiles or fibers made of aromatic polyesters, forexample, polyethylene terephthalates or condensation products obtainedfrom terephthalic acid and 1,4-bis-(hydroxymethyl)- cyclohexane. Dyeingsand prints of very good fastness properties are obtained on thesematerials, especially of very good fastness to light, washing adnthermofixing. The dyestuffs are characterised by a good atfinity to thefiber.

The dyestuffs are also suitable for the dyeing and printing of celluloseacetate and triacetyl cellulose and of fiber material of syntheticsuperpolyamide and polyacrylonitrile.

EXAMPLE 1 16.3 parts by weight 2-cyano-4-nitroaniline are dissolved at0-15 C. in 400 parts by weight of concentrated sulphuric acid, thesolution is diazotised, with good cooling and stirring, with 170 partsby volume nitrosyl-sulphuric acid (42 g. nitrite in 100 ml. H and themixture is poured on to about 3000 parts by weight of ice after about 3hours. A slight excess of nitrite is removed by means of amidosulphonicacid and the solution is sodium acetate. The dyestutf is filtered andwashed. In filtered. This solution is then combined witha solution ofthe dry state it is a dark powder which dissolves in 29.7 parts byWeight of an amino compound of the organic solvents, such as acetone oralcohol, with a formula blue colour. When brought into a fine dispersionby means 0 H, 5 of suitable additives, the dyestufi dyes fabrics ofacetate rayon in clear violet shades of good fastness to washing andlight.

1 H0O CH3 o Hio CzH4O (3011: The following dyestuffs can be obtained inthe same way 0 from the corresponding starting components; they dye themixture is partially neutralised with a dilute sodium 10 fabrics ofaromatic polyesters, such as polyethylene terhydroxide solution and thecoupling is completed with ephthalates, in the specified shades:

Shade 0211.0 0211.0 0 on, NHCOCH: 1;

l C2H40 (321140 C Cgl'lh NHCO OH; (H)

| oznioognioocmol nnooom H CgHa | NHCOCH: ltl) Red.

Cal s Violet.

Cl NHCOCH;

C2115 Red. a I CHCHQO CHgCHOCCHa NHC 0 CH3 1 l CH3 CH3 NHC 0 CH CH; NHCO OH:

used in some dyestuffs of the above examples as coupling component canbe obtained in the following manner:

1.2 moles B-chloro-fi-acetoxy diethyl ether and 1.2 moles of anhydroussodium acetate are added to 1 mole 1-N-ethyl-amino-3-acetyl-aminobenzeneat 120-140 C. in the course of 6 to 8 hours in such a manner that theamount of sodium acetate always remains somewhat deficient. Thecompletion of the reaction is established by chromatography. The base soobtained can be separated from the other reaction products by means ofwater and a mixture of methanol and water or it can be converted intothe dyestutf 'without further purification.

Other aromatic amines containing the group '-ITTC2H4OC2H4O fillRa R1 canbe obtained in the same manner. Dyeing is performed as follows:

250 grams of polyethylene terephthalate fibers are in- EXAMPLE 2 16.3parts by weight 2-cyano-4-nitroaniline are dissolved at 0-15" C. in 400parts by weight of concentrated sulphuric acid, the solution isdiazotised, with good stirring and cooling, with 170 parts by volumenitrosyl sulphuric acid (42 g. nitrite in 100 ml. H and the mixture ispoured on to about 3000 parts by weight of ice after about 3 hours. Aslight excess of nitrite is removed by means of amidosulphonic acid andthe solution is filtered. This solution is then combined with a solutionof 25.5 parts by weight of an amino compound of the formula CzHqOCzHqOHNHCO CH3 the mixture is partially neutralised with a dilute sodium Shadel 2 4O CzH40H ON NHC O CH;

C1 Red. i ICQIL; "@T

N I CzH OCzTl OH NHC O OH;

Br Blue.

I C2H4OC2H4OII N02 NHC 0 CH Cl 0 CH D I /C2 5 O21-F-N=N- N\ C2 4O02114011: ON

NHCONHz $11-15 ViOiOt.

G1 I C2H4OC2H4OH NHC 0 Q1320 CH (3311; Orange. i 021140 C2H OH CN NHC 0CH3 (E2115 Red.

' C2H4O C2TT4OH CN NBC 0 CH5 ("1 Red;

!0211 NC -N=N II I ([JN CzH O 021L011 NH0 0 CH3 C2115 Violet.

! 1 0211.0 CH CHOH Cl NH0 0 CH I C2135 O2N -N=N- -N\ R ed.

I CHCHQOCHgCHOH NHC 0 cm 1 CH CH3 CzH' Blue.

i C2H O 0211 011 N NH C O C H3 Shade CzHs NHCHO CZHiOCzHaOH N H C O CH;

H CN C2H5 g H OzN- CN=N N S CZH4O CHLOE NH C CH3 C-N 03H} Q n I. N\ CN=NN\ I S C 2H4 0 0 2114011 NHC 0 CH:

CzH4 O C 2H4O H C N NH O 0 CH8 C 1 O C H3 l l /CzH 0211 00215011 01 N HC O C H3 /CzHs CzH4O CrHiCHOH Cl NHC O OH;

C IIB 2 Z IO H CH3 NHCONHz Red:

Red:

Bluegreen.

Red.

Red.

Blueviolet.

Red;

Red.

Dyeing is performed as follows:

250 grams of polyethylene terephthalate fibers are introduced at C. intoa dyebath of 8 litres containing 4 g. of an emulsifying polyglycolether, 4 g. of the well dispersed dyestuff, 16 g. of a carrier, forexample, benzoic acid, and 20 g. diammonium phosphate. The bath isbrought to the boil within 30 minutes and dyeing is continued at thesame temperature for 1 /2 to 2 hours. The dyeing is subsequently washedalkaline at 70 C. for 20 minutes, rinsed and dried. A clear dyeing isobtained, which is fast to light and washing and is distinguished by agood fastness to thermofixing.

I claim:

1. A20 dyestuifs free from sulfonic acid and carboxylic acid groups ofthe formula in which R is phenyl substituted with cyano, nitro, chloro,bromo, acetyl, lower alkyl, lower alkoxy, trifiuoromethyl, carbomethoxy,methylamido, dimethylamido, carbobutoxy or lower alkyl sulfone, or aradical selected from the group consisting of nitroJhiazole,phenyl-thiadiazole, acetonitrothiophen, benzo-thiazole,methoxybenzothiazole, triazole and nitro-thiadiazole; X is an acylaminosubstituent selected from the group consisting of formylamino,amino-carbonylamino, lower alkyl carbonylamino, lower alkylsulfonylamino and lower alkyl carbonylamino substituted with chlorine; Yis hydrogen, lower alkyl or lower alkoxy; R is in which R is anunsubstituted or a substituted monoor dicyano-aniline said substituentsselected from the group consisting of chloro, bromo, lower alkyl, loweralkoxy, nitro and lower alkyl sulphone; X is lower alkyl carbonylaminoor lower alkyl sulphonylamino; Y is bydrogen, lower alkyl or loweralkoxy; R is methyl, ethyl or propyl; and R is a group CH CH OCH CH ORwherein R is selected from the group consisting of hydrogen and -CORwherein R is an unsubstituted or a substituted lower alkyl radical saidsubstituents being chloro, cyano, carbomethoxy or carboethoxy.

3. The azo dyestulf of claim 1 of the formula NHCOCHa 4. The azodyestuff of claim 1 of the formula 01 @Nl: 1 CN NHCO CH:

5. The azo dyestuif of claim 1 of the formula NO: NHCOCHs 6. The azodyestuff of claim 1 of the formula 1140 CzH4O C 0 CH3 7. The azodyestuff of claim 1 0f the formula C2H4O (321140 E NHC 0 CH3 8. The azodyestuff of claim 1 of the formula 1 02114002114011 NHCO CH3 ReferencesCited UNITED STATES PATENTS CHARLES B. PARKER, Primary Examiner C. F.WARREN, Assistant Examiner US. Cl. X.R.

